Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02041—Cleaning
  • H01L21/02057—Cleaning during device manufacture
  • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
  • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3218—Alkanolamines or alkanolimines
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

• the present invention relates generally to a cleaning composition and process for removal of organic, organometallic, and/or metallic residues from semiconductor substrates, and also to a composition which can be used to apply controlled and predetermined etch rates on selected metal substrates. More particularly, the present invention relates to compositions including 2-carbon atom linkage alkanolamines, in particular 2-(2-aminoethylamino)-ethanol (AEEA), which are useful for removing semiconductor device fabrication residues and in some embodiments a small predetermined amount of substrate from semiconductor-type substrates. The invention also includes the processes of using the compositions of the present invention to clean and/or etch substrates particularly containing exposed aluminum, titanium, copper, tungsten, and/or alloys thereof.
• Resists used to mask substrates such that patterned material can be added, need to be removed from substrates.
• a resist includes polymeric material, which may be crosslinked or hardened by baking. Therefore, a simple combination of solvents will often remove resists, though time and temperature constraints in the manufacturing process have in general moved the industry to slightly more aggressive compounds.
• compositions used for removing photoresists and other substrate layers have, for the most part, been highly flammable.
• reactive solvent mixtures can exhibit an undesirable degree of toxicity and are generally hazardous to both humans and the environment.
• these compositions are not only toxic, but their disposal is costly, since they must be disposed of as a hazardous waste.
• these prior art compositions generally have a severely limited bath life and, for the most part, are not recyclable or reusable.
• compositions for removing photoresists include inorganic alkalis in water, and polar organic solvents for positive photoresists.
• Polar organic solvents are used generally at temperatures below 50°C. Mixtures of alkanolamines in water can be used for most types of resists.
• compositions because many of the toxic components of such compositions are highly volatile and subject to unduly high evaporation rates, the compositions require special human and environmental safety precautions to be taken during storage and use of said compositions.
• the resists may in some locations be altered, for example by etching, into various compounds, which incorporate the altered resist, as well as some usually altered substrate.
• oxygen plasma oxidation is often used for removal of resists or other polymeric materials after their use, during the fabrication process has been completed.
• Such high energy processes typically result in the formation of organometallic and other residues, for example metal oxides, on sidewalls of the structures being formed in the fabrication process.
• Other etching including the use of directed energy and/or chemical etching, leave different types of residue, for example organometallic compounds and/or metal fluorides.
• direct layer deposition using convertible organometallic compounds which may or may not require etching to form a pattern, may leave yet other types of residues. These residues must be removed without substantially altering the underlying substrate.
• U.S. Patent No. 6,372,050 teaches a composition for cleaning residue from a substrate that contains 5 to 50% of a solvent selected from a particular group that includes M-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, and many others; 10 to 90% of an alkanolamine selected from diethyleneglycolamine (DGA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), AEEA, and mixtures thereof; from 0.1 to 10% of a carboxylic acid selected from formic acid, acetic acid, phthalic acid, salicylic acid, oxalic acid, and many others; and 1 to 40% water.
• a solvent selected from a particular group that includes M-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, and many others
• NMP M-methyl-2-pyrrolidone
• DMSO di
• a variety of metal and other layers are commonly employed in integrated circuit fabrication, including aluminum, aluminum/silicon/copper, copper, titanium, titanium nitride, titanium/tungsten, tungsten, silicon oxide, polysilicon crystal, and the like.
• the use of such different layers results in the formation of different organometallic residues in the high energy processes.
• a cleaning composition is often designed to be compatible with a single substrate exposed to the cleaning composition.
• EKC EKC Technology, Inc.
• Some of these compositions and processes are also useful for removing photoresist, polyimide, or other polymeric layers from substrates in integrated circuit fabrication, and EKC has also developed a variety of compositions and processes specifically for removing such polymeric layers from substrates in integrated circuit fabrication. Additionally, EKC has developed a variety of compositions and processes to selectively remove specific substrate compositions from a substrate surface at a controlled rate. Such compositions and processes are disclosed in the following commonly assigned issued patents:
• Triamine positive photoresist stripping composition and post-ion implantation baking Triamine positive photoresist stripping composition and post-ion implantation baking
• U.S. Patent o. 5,997,658 describes a remover for photoresist and etching residue that contains water, an amine, and a corrosion inhibitor including benzotriazole, gallic acid, or both.
• etching residue removal and substrate compatibility with chemicals employed in wet processing is becoming more and more critical for obtaining acceptable yield in very large scale integration (VLSI) and ultra large scale integration (ULSI) processes.
• VLSI very large scale integration
• ULSI ultra large scale integration
• the effectiveness of residue removal by etching depends on the composition of the surfaces or materials to be etched and the composition of the etchant, as well as many other variables too numerous to mention.
• the composition of such etching residue is generally made up primarily of the etched substrates, underlying substrate, etched and/or ashed photoresist, and etching gases.
• the substrate compatibility of the wafers with wet chemicals is highly dependent on the processing of the polysilicon, multilevel interconnection dielectric layers, and metallization in thin film deposition, etching and post-etch treatment of the wafers. Processing conditions are often quite different from one fabrication process to another, making it difficult to apply a particular composition to obtain both effective residue removal and substrate compatibility. For example, some compositions have produced corrosion on certain metal substrates, such as those including a titanium metal layer. Titanium has become more widely used in semiconductor manufacturing processes. It is employed both as a barrier layer to prevent electromigration of certain atoms and as an antireflector or refractory metal layer on top of other metals.
• HA Hydroxylamine
• Hydroxylamine formulations have also been useful in removing photoresists, such as is found in U.S. Patent Nos. 5,279,771 and 5,381,807, which describe formulations containing hydroxylamine, an alkanolamine, and optionally a polar organic solvent. Hydroxylamine formulations have also been useful in removing etching residue, such as is found in U.S. PatentNo. 5,334,332, which describes a formulation containing hydroxylamine, an alkanolamine, water, and a chelating agent. Hydroxylamine-containing formulations designed to remove residues are known to be aggressive to metals, particularly to titanium film and under more aggressive process conditions to aluminum film. As a result, various formulations have been developed to control the corrosion.
• the attack of titanium can be moderated by using different chelator, e.g. , such as disclosed in U.S. Patent No. 6,276,372, and /or by selecting a class of alkanolamine with 2-carbon linkage(s), which is disclosed, e.g., in U.S. Patent No. 6,121,217.
• other formulations include those disclosed in: U.S. Patent Nos. 6,276,372, 6,221,818, and 6,187,730, which each describe a hydroxylamine formulation with a gallic compound (as opposed to catechol) and an alcohol amine; U.S. Patent Nos. 6,242,400, which describes a hydroxylamine formulation with an alcohol amine and a polar organic solvent; U.S.
• Patent Nos. 6,156,661 and 5,981,454 which each describe a buffered hydroxyl-ffliine formulation with an organic acid
• U.S. Patent Nos. 6,140,287 and 6,000,411 which each describe a hydroxylamine formulation with an alkanolamine and a chelating agent
• U.S. PatentNo. 6,121,217 which describes a hydroxylamine formulation with an alkanolamine and gallic acid or catechol
• U.S. Patent No. 6,110,881 which describes a hydroxylamine formulation with an organic solvent, water, and a chelating agent
• U.S. Patent No. 5,997,658 to Peters et al. describes a hydroxlamine-free photoresist stripping and cleaning composition, for use particularly of copper or titanium substrates, having about 70 to 85% by weight of an alkanolamine, about 0.5 to 2.5% by weight of benzotriazole, about 0.5 to 2.5% by weight of gallic acid and the remainder being water.
• Alkanolamines include N-methylethanolamine (NMEA), monoethanolamine (MEA), diethanolamine, mono-, di-, and tri- isopropanolamine, 2-(2-aminoethylamino)- ethanol, 2-(2-aminoethoxy)-ethanol, triethanolamine, and the like.
• the preferred alkanolamine is N-methylethanolamine (MEA).
• U.S. Patent No. 5,928,430 to Ward et al entitled Aqueous stripping and cleaning compositions containing hydroxylamine and use thereof, describes an aqueous stripping composition comprising a mixture of about 55% to 70% by weight of a polar amine solvent, about 22.5 to 15% by weight of a basic amine, especially hydroxylamine, gallic acid as a corrosion inhibitor, and water.
• U.S. PatentNo. 5,419,779 to Ward describes a stripping composition containing water, 22.5 to 15% by weight of hydroxylamine, 55% to 70% monoethanolamine, and preferably up to about 10% by weight of a corrosion inhibitor, particularly one selected from the group consisting of catechol,
• the flash point is the lowest temperature at which a liquid can form an ignitable mixture in air near the surface of the liquid. The lower the flash point, the
• gasoline has a flash point of -40°C, and it is therefore more flammable than ethylene glycol which has a flash point of 111°C (232°F).
• Flammable liquids that are water miscible may have increased or decreased flash points when mixed with water. Often, the flash point of a mixture will be classified the same as that of the liquid with the lowest flash point.
• U.S. Patent 5,419,779 to Ward describes a process for removing an organic coating from a substrate by applying a composition consisting of about 62% by weight of MEA, about 19% by weight HA, a corrosion inhibitor which includes gallic acid and gallic acid esters, and water. This patent limits the operating temperature to between 40°C and
• compositions may change with time because they are generally stored for up to several days at operating temperatures during use.
• flash point of a mixture changes as certain components are distilled from the mixture.
• the cleaning and substrate etching characteristics of a formulation will change as the amounts of the components change.
• replenishing solutions consist essentially of water and, optionally, hydroxylamine and/or a hydroxylamine derivative.
• the replenishing solutions are preferably substantially free of alkanolamines and polar organic solvents, and optionally chelating agents and/or corrosion inhibitors.
• etch rates of most residue remover formulations increases with increasing process temperature. Some manufacturers suggest using formulations at low temperatures, such as at 30°C, to provide low etch rates at "normal" operating temperatures. Lower temperatures do not provide adequate removal of tougher residues, which may include polymeric material, within an feasible processing time.
• Fluoride-containing compositions can be used for oxide etch residue. This allows higher flashpoints for mixtures, in some cases exceeding 105°C.
• aluminum and titanium etch rates, at ambient temperatures, of 3 to 6 A/minute are found in commercial inhibited formulations. Therefore, higher temperatures are not practicable for such formulations.
• one object of the invention is to provide a family of photoresist and residue removing compositions which overcomes the above and other stated problems with the prior art. Another object of this invention is to provide an improved composition for residue removal and process using such a composition suitable for meeting current semiconductor fabrication requirements. It is another object of the invention to provide a process which is suitable for meeting the above objects.
• One embodiment of the invention is a residue removing composition which is effective for removing residues such as resists and etching residues after etching processes, e.g., plasma etching, which are undesired byproducts generated during the fabrication of integrated circuits on silicon wafers and similar processes, and also resists or other undesired materials, but does not attack the different underlying substrate metallurgies and insulation layers used in integrated circuit fabrication.
• residues such as resists and etching residues after etching processes, e.g., plasma etching, which are undesired byproducts generated during the fabrication of integrated circuits on silicon wafers and similar processes, and also resists or other undesired materials, but does not attack the different underlying substrate metallurgies and insulation layers used in integrated circuit fabrication.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, after etching processes, e.g., plasma etching, which residues can be undesired byproducts generated during the fabrication of integrated circuits on semiconductor wafers, but which composition does not aggressively attack underlying titanium and/or aluminum used in integrated circuit fabrication.
• residues such as resists and etching residues
• etching processes e.g., plasma etching
• One embodiment of the invention is a residue removing composition that, when used as an etchant or when used as a residue remover/etchant, provides a controlled slow etch rate on various substrates, in addition to cleaning any residues.
• One embodiment of the invention is a residue removing composition that, when used as an etchant or when used as a residue remover/etchant, provides a controlled slow etch rate on various substrates, in addition to cleaning any residues, wherein the etch rates on the different metal compositions are substantially the same, or alternatively differ in a predetermined amount.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which composition exhibits a low etch rate for a variety of metallic substrates while used at higher temperature, i.e., greater than 70°C, preferably greater than 90°C, for example in some instances greater than l l0°C.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which composition advantageously has a low formulation loss and a low composition change (excluding water and in some cases hydroxylamine), when stored and used at relatively higher temperatures.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which composition has a flash point in excess of 115°C, preferably in excess of 125°C, for example in excess of 130°C.
• Another embodiment of the invention is a residue removing composition that is effective for removing residues such as resists and etching residues and which contains less than 10%, preferably less than 5%, and more preferably is substantially free of components with a flash point below about 115°C, preferably below about 125°C, for example below about 130°C.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which composition contains less than 10%, preferably less than 5%, and more preferably is substantially free of organic components having a boiling point below about 199°C, preferably below about 215°C, for example below about 235°C.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which composition contains less than 10%, preferably less than 5%, and more preferably is substantially free of organic components having a boiling point not between about 199°C and 290°C, preferably between about 215°C and 290°C.
• One embodiment of the invention is a residue removing composition that is effective for removing residues, such as resists and etching residues, and which somposition contains less than 10%, preferably less than 5%, and more preferably is substantially free of organic components having a boiling point not between about 235°C and 260°C.
• One embodiment of the invention is a family of a residue removing compositions that contain AEEA and that are effective for removing residues, such as resists and etching residues, while being less aggressive to titanium and/or aluminum substrates than similar compositions with other alkanolamines different than AEEA.
• One embodiment of the invention is a family of solvent-based residue removing compositions that contain AEEA and that are effective for removing residues, such as resists and etching residues, while being useful for a variety of metallic and dielectric substrates, wherein the flash point of the cleaning composition is greater than about 120°C, preferably greater than about 125°C, more preferably greater than about
• One embodiment of the invention is a family of solvent-based residue removing compositions that contain AEEA and that are effective for removing residues, such as resists and etching residues, while being useful for a variety of metallic and dielectric substrates, wherein the flash point of the cleaning composition is greater than about 120°C, preferably greater than about 125°C, more preferably greater than about
• Another embodiment is a method of cleaning polymeric material, etching residue, or both from a semiconductor substrate, which method includes using the aforementioned family of solvent-based residue removing compositions in a process operated at a temperature between about 90°C and about 120°C.
• One embodiment of the invention is a family of solvent-based residue removing compositions that contain AEEA and that are effective for removing residues, such as resists and etching residues, while being useful for a variety of metallic and dielectric substrates, wherein the flash point of the cleaning composition is greater than about 125°C. Hydroxylamine does not have a reported flash point.
• Another embodiment of the invention is a multicomponent residue removing composition that is effective for removing residues, such as resists and etching residues, and that contains less than 10%, preferably less than 5%, and more preferably is substantially free of volatile organic components having a boiling point not between about 220°C and about 250°C. Hydroxylamine is not considered a volatile organic component for these purposes.
• Another embodiment of this invention is a family of residue removers that etch various substrates at a predetermined rate, for example etching aluminum, titanium, tungsten, and alloys thereof at approximately the same rate.
• Another embodiment of this invention a family of residue removers that etch various substrates at a predetermined rate, for example etching aluminum at a rate comparable to chemical mechanical etching solutions, but are not aggressive to other selected metals, for example titanium and alloys thereof.
• Another embodiment of the invention is a composition and process that is suitable for removing residues from wafers and other substrates including one or more metal or metal alloy layers without substantial attack on such layers.
• a residue removal and/or etching composition in accordance with this invention includes 2-(2-aminoethylamino)-ethanol (AEEA), which is an alcohol amine compound that has a relatively high boiling point, a relatively high flash point, and a relatively low (in some cases, non-existent) etch rate under standard process conditions for metallic substrates or layers.
• AEEA 2-(2-aminoethylamino)-ethanol
• the attainment of these and related objects may be achieved through use of the residue removal and/or etching composition comprising a derivative of 2-(2-aminoethylamino)-ethanol formed by adding substituting groups onto a 2-(2-aminoethylamino)-ethanol base.
• a process for removing a residue from a substrate and/or for etching a metal or metal alloy on a substrate includes contacting the substrate with a composition that contains a two-carbon atom linkage alkanolamine compound, particularly 2-(2-aminoethylamino)-ethanol, for a time and at a temperature sufficient to remove the residue from the substrate and/or to selectively etch the metal and/or metal alloy from the substrate.
• a composition that contains a two-carbon atom linkage alkanolamine compound particularly 2-(2-aminoethylamino)-ethanol
• FIGS. 1- 19 are scanning electron microscope (SEM) photographs showing comparative results achieved using selected embodiments of compositions and processes of the present invention, as described in the examples herein.
• composition contains less than 0.2%, preferably less than about 0.1%, most preferably less than about 0.01%, of the specific element mention thereafter; and for trace contaminants such as metal ions, substantially free is defined in the specification, t ' .e., less than 10 ppm metals and metal ions.
• the composition is completely free of any added element specifically mentioned thereafter, or at least does not contain the added element in an amount such that the element affects the efficacy, storability, usability regarding necessary safety concerns, or stability of the composition.
• a compound should generally not be characterized under more than one enumerated element of the composition according to the invention. If a compound is capable of being characterized under, for example, two enumerated embodiments of the composition, such a compound may be characterized herein only under either one of the two enumerated elements, but not under both. At times, the distinction may be made based on the content of the compound in the composition. For instance, catechol or gallic acid can act primarily as a corrosion inhibitor at "high" concentrations, i.e. about 0.5% to 20%, or primarily as a metal chelator at "low" concentrations, . e. , in the ppm to 0.5 wt% range.
• hydroxylamine and hydroxyamine derivatives are not considered organic, despite the organic substituents that may be present on substituted hydroxylamine.
• compositions according to a preferred embodiment of this invention contain AEEA.
• compositions according to embodiments of this invention contain a derivative of AEEA, wherein the derivative is obtained by substituting a polar and/or non-polar moiety or moieties onto an AEEA base.
• the AEEA and or AEEA derivative can be present in an amount ranging from about 1 % to about 99%, though in most instances the amount ranges from about 10% to about 85%.
• AEEA range given for various compositions described herein, there is a "high- AEEA” embodiment where the amount of AEEA is in the upper half of the range, and a “low-AEEA” embodiment where AEEA is present in an amount bounded by the lower half of the range.
• the higher AEEA embodiments exhibit lower etch rates than the low AEEA embodiments for selected substrates, especially aluminum and titanium.
• compositions also include other compounds, particularly polar organic solvents, water, alkanolamines, hydroxylamines, chelating agents, and/or corrosion inhibitors.
• a preferred alkanolamine is a two carbon atom linkage alkanolamine.
• the generic two carbon atom linkage alkanolamine compounds suitable for inclusion in the invention have the structural formula,
• R h R x ', R 2 , R 2 ', and R 3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; wherein Z is a group having the formula -(-Q-CR 1 R 1 '-CR 2 R 2 , -) m -, such that m is a whole number from 0 to 3 (i. e.
• R l9 R , R 2 , and R 2 ' may be independently defined in each repeat unit, if m>l, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>l, each Q being independently either -O- or -NR 3 -; and wherein X and Y are, independently in each case, hydrogen, a C C 7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CR !
• R -CR 2 R 2 '-Z-F with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R l5 R , R 2 , R 2 ', and R 3 above, and with Z, R l5 Rj', R 2 , R 2 ', and R 3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the composition contains a two-carbon atom linkage alkanolamine compound, in which m is greater than or equal to 1.
• the composition contains a two-carbon atom linkage alkanolamine compound, in which m is 1 and R l9 R,', R 2 , R 2 ', and R 3 are all hydrogen or a C C 4 linear or branched hydrocarbon.
• the composition contains a two- carbon atom linkage alkanolamine compound, in which: m is 1 ; R l5 R , R 2 , R 2 ', and R 3 are all hydrogen or a C x -C 4 linear or branched hydrocarbon; and Q is -NR 3 .
• the composition contains a two-carbon atom linkage alkanolamine compound, in which: m is 1; RNase R , R 2 , R 2 ', and R 3 are all hydrogen; X and Y are, independently, hydrogen or a linear or branched C C 4 hydrocarbon; and Q is -NH-, -NCH 3 -, or -N[(C 2 -C 4 ) linear or branched hydrocarbon]-.
• the operating temperature was previously near or above the flash point of the composition mixture.
• the operating temperature was given as approximately 100°C, and in the case of monoethanolamine-catechol- hydroxylamine-water compositions described in U.S. PatentNo. 5,419,779, was approximately 90°C.
• the operating temperature is advantageously restricted to about 10- 15 °C below the flash point of the composition.
• the presently described compositions having relatively high flash points in comparison to prior art compositions, allow more latitude in selecting an operating temperature within a safe range. Additionally, compounds with lower boiling points would be distilled from prior art compositions over time, resulting in off-specification cleaners, special make-up solutions, or both.
• the two carbon atom linkage alkanolamine compounds useful in the present invention preferably have relatively high boiling points (e.g., 185°C or above, preferably 200°C or above, alternately 215°C or above) and preferably have relatively high flash points (e.g., 95 °C or above, preferably 100°C or above, alternately 110°C or above).
• relatively high boiling points e.g., 185°C or above, preferably 200°C or above, alternately 215°C or above
• relatively high flash points e.g., 95 °C or above, preferably 100°C or above, alternately 110°C or above.
• Preferred specific examples of such two carbon atom linkage alkanolamine compounds include AEEA and 2-(2-aminoethoxy) ethanol (“DGA").
• compositions according to the invention contain
• AEEA a derivative of AEEA, or both, though preferably at least AEEA.
• the composition according to the invention contains a mixture of two or more individual two-carbon atom linkage alkanolamine compounds, which preferably consist essentially of AEEA, at least a second two-carbon atom linkage alkanolamine compound other than AEEA, and optionally a corrosion inhibitor and or a chelator.
• AEEA is a preferred component of the compositions of the present invention, in part because of its physical properties and in part because of its surprising and unexpected low corrosion rates, particular found when admixed into cleaning compositions described herein.
• AEEA has an advantage over most other alkanolamines disclosed in the prior art, due to its higher boiling point and flash point, as shown by the following data gathered from the Aldrich Chemical Catalog (2001-2002) and the Hawley's Condensed Chemical Dictionary (Twelfth Edition). Higher flash point and/or boiling point allows longer bath life usage, due to lower evaporation rates. Additionally, higher flash point and/or boiling point allows for safer operation at standard working conditions, and also for use of the composition at increasingly elevated temperatures.
• AEEA is also a nucleophilic amine and is a two carbon atom linkage alkanolamine, and AEEA contains two nitrogen molecules that allow it to form more stable complexes with etching residues.
• EKC Technology has developed numerous formulations that contain alkanolamines such as DGA. We have surprisingly found that the use of AEEA in a weight-for- weight substitution with DGA or other alkanolamines in these solutions can significantly lower the aggressiveness of the resulting formulation towards both titanium and aluminum without adversely affecting its cleaning ability.
• Ti etch rate A [Alkanolamine] + B [Hydroxylamine] + ....
• a and B are regression coefficients relating to each of the components of the composition.
• the units can be in weight %, but similar results are found when expressed as molar %, because the molecular weights of AEEA and diglycolamine (DGA) are virtually identical.
• the etch units can be in A/min, and the experimental data from which this equation was derived was obtained at a temperature of about 70°C.
• This equation is only a linear regression providing a first-order treatment. Such a equation ignores synergy in the chemistry.
• the first-order treatment is a good approximation to real world situations. Higher order fits start to lose (chemical) meaning. If measuring an etch rate, having (non-chemically obvious) synergistic interactions between two liquid components and the etched surface, where neither of the components passivates the surface of the substrate, constitutes a situation akin to a "three-body” collision, which is practically very rare. Therefore, the first order formulas for etch rate of substrate;
• Al etch rate Y [AEEA] + Z [Diglycolamine] + C [Hydroxylamine] * ...
• a formulation is developed by altering the composition to achieve a non-zero, positive etch rate for a plurality of materials on a surface of a substrate, wherein the etch rates are both low and substantially equal for each of the substrate metals encountered on a semiconductor surface.
• the formulation can be tailored to provide a small etch rate to each compound, wherein the etch rates for each of the selected substrates exposed to the formulation are within, for example, 50% of one another, preferably within 20% of one another. It may be necessary to add a corrosion inhibitor, for example catechol, to achieve similar etch rates for aluminum and titanium.
• the manufacturer may wish to etch only selected substrates, and the formulation can also be adjusted to meet these criteria.
• One embodiment of this invention shows no etching of titanium and severe etching of aluminum.
• the formulations of the present invention can be stable for long periods of time, i.e., for at least 2 or 3 days, when exposed to normal operating or process conditions.
• normal operating conditions we mean between about 50 and 100°C, for example between 60 and 75°C.
• stable we mean the corrosion characteristics on various metal substrates is relatively unchanging.
• water can be added to the formulation, but is in some cases not added to the formulation. This requires the boiling points and/or the flash points of the alkanolamines be selected so that the formulation does not substantially change composition during use. High boiling point alkanolamines are, therefore, the preferred component to vary when tailoring the cleaner/etcher composition to the plurality of substrates .
• Examples of other two-carbon atom linkage alkanolamine compounds include, but are in no way limited to, DGA, 2-aminoethanol ("monoethanolamine” or “MEA”), 2-(N-methylamino) ethanol (“monomethyl ethanolamine” or “MMEA”), 2-amino- 1-propanol (“monoisopropanolamine” or “MIPA”), 2-(N-hydroxyethyl-amino)-ethanol (“diethanolamine” or “DEA”), 2- [(2-aminoethyl)-(2-hydroxyethyl)-amino] -ethanol (“N,N- bis-hydroxyethyl-emylenediamine"), N,N,N-tris-(2-hydroxyethyl)-ammonia (“triethanolamine” or "TEA”), N-aminoethyl-N'-hydroxyethyl-ethylenediamine, N,N'- dihydroxyethyl-ethylenediamine, 2- [2-(2-
• the compositions according to the invention optionally contain a chelating agent.
• the composition according to the invention contains a single chelating agent, which is preferably EDTA (or a non-metallic salt thereof), gallic acid, or catechol.
• Catechol has a boiling point of 245°C, and a flash point of 127°C.
• the corrosion inhibitor can be resorcinol, with a boiling point of 281°C and a flash point of 127°C.
• the composition according to the invention contains a mixture of two chelating agents, preferably catechol and gallic acid.
• the composition according to the invention contains a mixture of two chelating agents, preferably catechol and EDTA.
• the composition is substantially free from chelating agents.
• chelating agents include, but in no way limited to, mono-, di-, or multi- hydroxybenzene-type compounds, e.g., such as catechol, resorcinal, butylated hydroxytoluene ("BHT"), and the like, or a combination thereof.
• the chelators include three or more carboxylic acid-containing moieties, e.g., such as ethylenediamine tetraacetic acid (“EDTA”), non-metallic EDTA salts, and the like, or a combination thereof.
• EDTA ethylenediamine tetraacetic acid
• Compounds containing a two carboxylic acid moieties, such as citric acid are less preferred.
• Aromatic compounds containing thiol groups e.g., such as thiphenol; amino-carboxylic acids; diamines, e.g., such as ethylene diamine; polyalcohols; polyethylene oxide; polyamines; polyimines; or a combination thereof, are useful in one embodiment.
• two or more chelating agents can be used in one composition, where the chelating agents are selected from groups described above. Alternately or additionally, some chelating agents are described in U.S. Patent No. 5,417,877, issued May 23, 1995 to Ward, and in commonly assigned U.S. PatentNo. 5,672,577, issued September 30, 1997 to Lee, the disclosures of each of which are incorporated herein by reference.
• compositions according to the invention optionally contain a corrosion inhibitor.
• the composition according to the invention contains a single corrosion inhibitor, which is preferably choline hydroxide, bischoline hydroxide, or trischoline hydroxide.
• the composition according to the invention is substantially free from corrosion inhibitors.
• corrosion inhibitors include, but are not limited to, nitrate salts of ammonium; hydrocarbon-substituted ammonium nitrate salts; benzotriazole; 2,4- pentandione dioxime; l,6-dioxaspiro[4,4] nonane 2,7-dione (di-ether); thiourea; ammonium bisulfite; choline bisulfite; choline hydroxide; bischoline hydroxide; trischoline hydroxide; glycerol; sorbitol; gelatine; starch; phosphoric acid; silicic acid; polyethylene oxide; polyethylene imine; and the like; or a combination thereof.
• the corrosion inhibitors are substantially free of metals and/or metal ions.
• Catechol can, in one embodiment, act as both a chelating agent and as a corrosion inhibitor.
• the compositions according to the invention optionally contain a salt of hydrofluoric acid and a base that is substantially free from metal ions (hereinafter "HF-base salt,” without intent to limit).
• HF-base salts include, but are in no way limited to, ammonium fluoride, diisopropylethylammonium fluoride, ammonium bifluoride, pyridinium fluoride, amine fluorides, and the like, or a combination thereof.
• the HF-base salt includes diisopropylethylammonium fluoride or ammonium fluoride.
• Such compositions advantageously include AEEA, a corrosion inhibitor, and optionally a polar organic solvent. Most formulation described herein are preferably free of fluoride ions, however, so, in an alternate embodiment, the composition according to the invention is substantially free from HF-base salts.
• compositions according to the invention also contain hydroxylamine or a derivative thereof, which satisfies the general formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• hydroxylamine examples include, but are in no way limited to, hydroxylamine, N-methyl-hydroxylamine, N,N- dimethyl-hydroxylamine, N-ethyl-hydroxylamine, N,N-diethyl-hydroxylamine, methoxylamine, ethoxylamine, N-methyl-methoxylamine, and the like.
• hydroxylamine is not an organic, and the boiling point and flash point of hydroxylamine and hydroxylamine derivatives is of no consequence to the formulation.
• hydroxylamine and its derivatives are available (and may be included in a composition according to the invention) as salts, e.g., sulfate salts, nitrate salts, or the like, or a combination thereof, and the invention includes these forms of hydroxylamine compounds and their derivatives. These salts greatly increase the theoretical flash point of hydroxylamine derivatives. Therefore, in another embodiment, the composition contains hydroxylamine, a sulfate or nitrate salt of hydroxylamine, or a combination thereof. Hydroxylamines are not desired in a subset of the formulations described herein. Therefore, in some embodiments, the composition according to the invention is substantially free from hydroxylamine and/or derivatives thereof.
• the composition according to the invention optionally contains water. Water is preferred in a majority of residue removing compositions. Additionally, HA is commercially available in an aqueous, i.e., a 50% aqueous, solution. Hydroxylamine derivatives are typically available in more concentrated aqueous forms, for example 85% solutions with 15% water. However, hydroxylamine and/or hydroxylamine derivatives can be obtained or manufactured, in some instances and in some concentrations, in a water-free formulation. As described above, in an alternate embodiment, the composition according to the invention is substantially free from water. In one embodiment, the composition according to the invention optionally contains a polar organic solvent.
• polar organic solvents for the composition according to the invention include, but are in no way limited to, dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted pyrrolidone such as N-methyl-2-pyrrolidone (NMP), sulfolanes, dimethylacetamide, and the like, or any combination thereof.
• Dimethylsulfone, CAS No. 126-33-0 with a boiling point of 237°C, is preferred in some embodiments of the invention.
• NMP with a boiling point of 199-202°C and a flash point of only 96°C, may be useful in some embodiments because of low cost. NMP does, however, tend to lower the flash point of mixtures of the present invention. Similarly, DMSO, with a boiling point of 189°C and a flash point of only 95°C, is less preferred in some embodiments of the invention. 2,4-dimethylsulfolane, with a boiling point of 280°C and a flash point of 143°C, is preferred in some embodiments of the invention. Care must be taken because, in the absence of alkanolamines and the like, 2,4- dimethylsulfolane is only slightly miscible with water.
• amines particularly alkanolamines and also particularly low molecular weight amines
• a polar organic solvent can also be used in the composition of the present invention.
• additional polar organic solvents as known in the art, other than those specifically excluded, can also be used in the composition of the present invention.
• the composition according to the invention is substantially free from polar organic solvents as defined herein.
• non-polar organic solvents are not preferred, though high boiling alcohols and the like may be used.
• Organic solvents including polar organic solvents, that have a boiling point less than about 100°C are undesirable in the composition according to the invention, as they tend to evaporate over a period of more than about 24-48 hours at operating conditions.
• the composition according to the invention be substantially free of organic solvents that have a boiling point less than about 100°C. It is more preferred that the composition according to the invention be substantially free of organic solvents that have a boiling point less than about 150°C. It is even more preferred that the composition according to the invention be substantially free of organic solvents that have a boiling point less than about 199°C.
• the composition according to the invention optionally contains an amine compound that is not a hydroxyl-containing amine and is not an alkanolamine.
• amine compounds include, but are in no way limited to, o- diaminobenzene, p-diaminobenzene, N-(2-aminoethyl)-ethylenediamine (“AEEDA”), piperazine, N-substituted piperazine derivatives, piperidine, N-substituted piperidine derivatives, diethylene triamine, 2-methyleneaminopropylenediamine, hexamthylene tetramine, and the like, or a combination thereof.
• AEEDA 2-aminoethyl-ethylenediamine
• the non-hydroxyl-containing amine compound(s) has(have) a boiling point no less than about 100°C, or alternately no less than about 150°C. Amines may increase corrosion of certain sensitive metals.
• the composition according to the invention is substantially free from non-hydroxyl-containing amine compounds, or non- hydroxyl-containing amine compounds having boiling points no less than about 100°C, or
• the composition according to the invention also contains a surfactant.
• surfactants include, but are in no way limited to, sodium laurel sulfate, sodium stearate, and the like, or a combination thereof.
• compositions according to the invention contain a
• two-carbon atom linkage alkanolamine compound (preferably including, and alternately consisting essentially of, AEEA) in an amount from about 1% to about 98%, alternately from about 5% to about 90%, from about 10% to about 85%, from about 20% to about 80%, or from about 30% to about 70%.
• composition according to the invention contains
• composition according to the invention contains a two-carbon atom linkage alkanolamine AEEA compound in an amount from about 50% to about 99.9%, alternately from about
• composition of the present invention consists essentially of AEEA and water. In another embodiment the composition of the present invention consists essentially of AEEA, water, and a chelating agent. In another
• composition of the present invention consists essentially of AEEA, water, and a corrosion inhibitor
• composition of the present invention consists essentially of AEEA, water, a chelating agent, and a corrosion inhibitor which is different from the chelating agent.
• the corrosion inhibitor and chelator are selected such that neither primarily performs both
• composition of the present invention consists essentially of AEEA, a second two carbon atom linkage alkanolamine, and water.
• composition of the present invention consists essentially of AEEA, a second two carbon atom linkage alkanolamine, water, and a chelating agent.
• composition of the present invention consists essentially of AEEA, a second two carbon atom linkage alkanolamine, water, and a corrosion inhibitor.
• composition of the present invention consists essentially of AEEA, a second two carbon atom linkage alkanolamine, water, a chelating agent, and a corrosion inhibitor which is different from the chelating agent.
• the corrosion inhibitor and chelator are selected such that niether primarily performs both functions.
• AEEA:alkanolamine ratio When one or more two-carbon atom linkage alkanolamine compounds other than AEEA are included in the composition according to the invention, they can advantageously be present in an amount such that the ratio between the AEEA and other two-carbon atom linkage alkanolamine compound (hereinafter "AEEA:alkanolamine ratio,” without any intent to limit) is from about 20: 1 to about 1 :20. In one embodiment, the AEEA:alkanolamine ratio is from about 15:1 to about 1:1, alternately from about 10:1 to about 1.5: 1 , for example, from about 4: 1 to about 2:1.
• the AEEA:alkanolamine ratio is from about 1 :1 to about 1:15, alternately from about 1 : 1.5 to about 1:10, for example, from about 1 :4 to about 1:2.
• the AEEA:alkanolamine ratio is pre-selected to provide a desired rate of etching of a particular metal or metals and/or metal alloy or alloys layer, or portion thereof, on a particular substrate or substrates.
• the amount of chelating agent in the composition according to the invention can advantageously be from about 0.01% to about 15%, preferably from about 0.1% to about 10%), for example, from about 2% to about 5%, or alternately from about 0.01% to about 0.1%.
• the amount of corrosion inhibitor in the composition according to the invention can advantageously be from about 0.1% to about 10%, preferably from about 1% to about 5%.
• the amount of HF-base salt in the composition according to the invention can advantageously be from about 0.01% to about 20%, for example, from about 0.1% to about 5%, or alternately from about 1% to about 10%.
• a composition containing HF-base salt and AEEA is preferably substantially free from polar organic solvent, and may optionally contain one or more of the following: one or more additional two-carbon atom linkage alkanolamine compounds; one or more chelating agents or corrosion inhibitors; or water.
• composition according to the invention can advantageously be from about 0.1% to about 50%, preferably from about 1% to about 25%, more preferably from about 5% to about 20%, alternately from about 1% to about 10% or from about 10% to about 20%.
• the amount of water in the composition according to the invention can advantageously be from about 1% to about 50%, preferably from about 2% to
• the amount of polar organic solvent in the composition according to the invention can advantageously be from about 1% to about 75%, for example from about 5% to about 50%, or alternately from about 0.1% to about 45%, for example
• the composition may contain at least about 10% by weight, preferably from about 10% to about 80%, of at least one two carbon atom linkage alkanolamine compound, from about 5% to about 40% by weight, preferably from about 5% to about 30%, of gallic acid, catechol or other chelating agent, and optionally, up to about
• the balance of the composition can compose water, preferably high purity deionized water, or a suitable polar organic solvent or mixture thereof. In one embodiment this composition is substantially free or water, polar organic solvents, or both.
• the chelating agent when present, enhances the ability of the two carbon atom linkage alkanolamine compound to remove the residue.
• the catechol, gallic acid, or chelating agent can help to prevent attack on the metal or metal alloy substrate, e.g., titanium.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition contains 2-(2-aminoethylamino)-ethanol and water.
• this composition can be substantially free from one or more of the following: polar organic solvents; organic
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms
• X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• aqueous amines corrode metal, for example when washing off cleaning compositions.
• a composition consisting essentially of AEEA and water removes residue and does not promote corrosion of Ti or Al.
• such a composition has greater than about 60% AEEA, more preferably greater than about 70% AEEA, and even more preferably greater than about 80% AEEA.
• a composition containing about 85 to about 95% AEEA can both remove residue and not promote corrosion even when washed off with water. It is believed that a composition consisting essentially of AEEA can be used to remove residue, especially from substrate surfaces comprising Ti, Al, Cu, W, or mixtures or alloys thereof.
• the above described compositions further comprise a chelating agent and/or a corrosion inhibitor. In one embodiment, the above described compositions further comprise a salt of hydrofluoric acid and a base that is substantially free from metal ions, and optionally a chelating agent and/or a corrosion inhibitor. In another embodiment, any of the above described compositions further comprise a second chelating agent and/or a corrosion inhibitor.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition contains 2-(2-aminoethylamino)-ethanol, water, and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• R 3 can be hydrogen and X and Y can be, independently, hydrogen or a linear hydrocarbon containing from 1 to 3 carbon atoms.
• compositions can also be substantially free from one or more of the following: polar organic solvent; organic solvent; surfactants; chelating agents and/or corrosion inhibitors; non-hydroxyl-containing amines; or a salt of hydrofluoric acid and a base that is substantially free from metal ions.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition contains: 2-(2-aminoethylamino)-ethanol; a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having the structural formula,
• R -CR 2 R 2 '-Z-F with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R l5 R , R 2 , R 2 ', and R 3 above, and with Z, R l5 Rj', R 2 , R 2 ', and R 3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring; and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• R 3 can be hydrogen and X and Y can be, independently, hydrogen or a linear hydrocarbon containing from 1 to 3 carbon atoms.
• the two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol has a flash point greater than about 100°C, preferably greater than 130°C, and/or a boiling point greater than about 200°C, preferably greater than 220°C, and is present in an amount less than about 35% by weight of the composition.
• the above compositions may be substantially free from one or more of the following: polar organic solvent; organic solvent; surfactants; chelating agents and/or corrosion inhibitors; non-hydroxyl-containing amines; and a salt of hydrofluoric acid and a base that is substantially free from metal ions.
• the weight ratio of AEEA to the two carbon atom linkage alkanolamine compound other than AEEA is more than about 1:1.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition consists essentially of: 2-(2-aminoethylamino)-ethanol; a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having the structural formula,
• R l5 R , R 2 , R 2 , and R 3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; wherein Z is a group having the formula -(-Q-CR ⁇ R,'-CR 2 R 2 '-) m -, such that m is a whole number from 0 to 3 (i. e.
• R R.', R 2 , and R 2 ' may be independently defined in each repeat unit, if m>l, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>l, each Q being independently either -O- or -NR 3 -; and wherein X and Y are, independently in each case, hydrogen, a C ⁇ -C 7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CR !
• R -CR 2 R 2 '-Z-F with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R l5 R , R 2 , R 2 ', and R 3 above, and with Z, R i5 Ri', R 2 , R 2 ', and R 3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring; and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition consists essentially of: 2-(2-aminoethylamino)-ethanol; a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having a boiling point greater than about 200°C, having a flash point of greater than about 100°C, preferably 120°C, and having the structural formula,
• R l9 R ⁇ R 2 , R 2 ', and R 3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; wherein Z is a group having the formula -(-Q-CR ⁇ R ⁇ '-CR 2 R 2 '-) m -, such that m is a whole number from 0 to 3 (i. e.
• R l9 R , R 2 , and R 2 ' may be independently defined in each repeat unit, if m>l, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>l, each Q being independently either -O- or -NR 3 -; and wherein X and Y are, independently in each case, hydrogen, a C j -Cy linear, branched, or cyclic hydrocarbon, or a group having the formula -CRj R ⁇ -CR, R 2 '-Z-F, with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R l9 R , R 2 , R 2 ', and R 3 above, and with Z, R l5 R,', R 2 , R 2 ', and R 3 defined as above,
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and or metal alloy portions and/or layers, wherein the composition consists essentially of: 2-(2-aminoethylamino)-ethanol; a first two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having the structural formula,
• each of the two carbon atom linkage alkanolamine compounds has a boiling point greater than about 190°C, preferably greater than about 200°C, more preferably greater than about 225°C, and a flash point of greater than about 95°C, preferably greater than about 100°C, more preferably greater than about 130°C.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition consists essentially of 2-(2-aminoethylamino)-ethanol, water, and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition consists essentially of
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition consists essentially of 2-(2-aminoethylamino)-ethanol, water, hydroxylamine, and a corrosion inhibitor, for example catechol.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition includes 2-(2-aminoethylamino)-ethanol, less than about 50% by weight of a polar organic solvent, gallic acid, and optionally a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having the structural formula,
• Rstrich R , R 2 , R 2 ', and R 3 are, independently in each case, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; wherein Z is a group having the formula -(-Q-CR 1 R ⁇ '-CR 2 R 2 '-) rn -, such that m is a whole number from 0 to 3 (i. e.
• R l9 R , R 2 , and R 2 may be independently defined in each repeat unit, if m>l, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>l, each Q being independently either -O- or -NR 3 -; and wherein X and Y are, independently in each case, hydrogen, a C r C 7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CRi R -CR;- R 2 '-Z-F, with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R u Rj 1 , R 2 , R 2 , and R 3 above, and with Z, R 1?
• each of the two carbon atom linkage alkanolamine compounds has a boiling point greater than about 190°C, preferably 220°C, and a flash point of greater than about 95°C, preferably greater than about 120°C.
• the two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol has a flash point greater than about 100°C and/or a boiling point greater than about 200°C, and is present in an amount less than about 10% by weight of the composition.
• the above described compound may also optionally contain water and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the above described compound may also optionally contain a non-hydroxyl- containing amine compound. However, in many embodiments the compositions are substantially free of such amines.
• compositions may be substantially free from one or more of the following: non-polar organic solvent; surfactants; non-hydroxyl-containing amines; a salt of hydrofluoric acid and a base that is substantially free from metal ions; water; and hydroxylamine and/or a hydroxylamine derivative, as defined above.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition includes 2-(2-aminoethylamino)-ethanol, less than about 50% by weight of a polar organic solvent, a dihydroxybenzene compound (e.g., including catechol), and optionally a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol, having the structural formula,
• each of the two carbon atom linkage alkanolamine compounds has a boiling point greater than about 190°C and a flash point of greater than about 95°C.
• the two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol has a flash point greater than about 100°C and/or a boiling point greater than about 200°C, and is present in an amount less than about 10% by weight of the composition.
• the above described compound may also optionally contain water and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the above described compound may also optionally contain a non-hydroxyl- containing amine compound.
• the above compositions may be substantially free from one or more of the following: non-polar organic solvent; surfactants; non-hydroxyl-containing amines; a salt of hydrofluoric acid and a base that is substantially free from metal ions; water; and hydroxylamine and/or a hydroxylamine derivative, as defined above.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition includes 2-(2-aminoethylamino)-ethanol, 2-(2-aminoethylamino)-ethylamine, and optionally a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)- ethanol, having the structural formula,
• R , R 2 , and R 2 ' may be independently defined in each repeat unit, if m>l, within the parameters set forth for these moieties above, and Q may be independently defined in each repeat unit, if m>l, each Q being independently either -O- or -NR 3 -; and wherein X and Y are, independently in each case, hydrogen, a Cj-C 7 linear, branched, or cyclic hydrocarbon, or a group having the formula -CRj R ⁇ '-CR 2 R 2 '-Z-F, with F being either -O-R 3 or -NR 3 R 4 , where R 4 is defined similarly to R t , R , R 2 , R 2 , and R 3 above, and with Z, R l5 R ] ', R 2 , R 2 ', and R 3 defined as above, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• each of the two carbon atom linkage alkanolamine compounds has a boiling point greater than about 190°C, for example greater than about 220°C, and a flash point of greater than about 95°C, more preferably greater than about 125°C.
• the two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol has a flash point greater than about 130°C and/or a boiling point greater than about 230°C, and is present in an amount less than about 40% by weight of the composition.
• the above described compound may also optionally contain water and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the above described compound may also optionally contain a chelating agent and/or a corrosion inhibitor.
• the above described compound may also optionally contain another non- hydroxyl-containing amine compound, other than 2-(2-aminoethylamino)-ethylamine (which is already present).
• compositions may be substantially free from one or more of the following: non-polar organic solvent; surfactants; a salt of hydrofluoric acid and a base that is substantially free from metal ions; water; and hydroxylamine and/or a hydroxylamine derivative, as defined above.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition includes 2-(2-aminoethylamino)-ethanol, from about 25% to about 75% by weight of a polar organic solvent, from about 13% to about 50% by weight of ethylenediamine- tetraacetic acid or an mono-, di-, tri-, or tetra- ammonium salt thereof, optionally from about 0.15% to about 10% by weight of an ammonium salt (e.g., tartrate, citrate, formate, gluconate, nitrate, thiosulfate, persulfate, bicarbonate, phosphate, fluoride, and the like, or a combination thereof), optionally from about 5% to about 75% water, and optionally a two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamin
• each of the two carbon atom linkage alkanolamine compounds has a boiling point greater than about 190°C, preferably greater than about 220°C, and a flash point of greater than about 95°C, preferably greater than about 120°C.
• the two carbon atom linkage alkanolamine compound other than 2-(2-aminoethylamino)-ethanol has a flash point greater than about 130°C and/or a boiling point greater than about 230°C, and is present in an amount less than about 10% by weight of the composition.
• the above described compound may also optionally contain water and hydroxylamine and/or a hydroxylamine derivative, having the structural formula:
• R 3 is hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms; and wherein X and Y are, independently, hydrogen or a linear, branched, or cyclic hydrocarbon containing from 1 to 7 carbon atoms, or wherein X and Y are linked together form a nitrogen-containing heterocyclic C 4 -C 7 ring.
• the above described compound may also optionally contain a non-hydroxyl- containing amine compound.
• compositions may be substantially free from one or more of the following: non-polar organic solvent; surfactants; non-hydroxyl-containing amines; a salt of hydrofluoric acid and a base that is substantially free from metal ions, other than ammonium fluoride (which is already present); water; and hydroxylamine and/or a hydroxylamine derivative, as defined above.
• the present invention relates to a composition which is capable of removing organic, organometallic, and/or metal oxide residues from substrates comprising metal and/or metal alloy portions and/or layers, wherein the composition includes 2-(2-aminoethylamino)-ethanol, from about 2% to about 80% by weight of a polar organic solvent (e.g., dimethylacetamide), from about 0.1% to about 3% by weight of ammonium fluoride, and optionally from about 2% to about 85% water.
• a polar organic solvent e.g., dimethylacetamide
• all of the compositions according to the invention have very low metal impurity/ion contents, i.e., less than about 10 ppm total.
• the compositions according to the invention have less than about 5 ppm total metal content, preferably not more than about 1 ppm total metal impurity and metal ion content.
• the residue cleaning compositions of the present composition are effective in removing organometallic and selected metal oxide residue from a variety of integrated circuit constructs on substrates, e.g. : silicon; SiGe; Group III-V compounds, such as GaAs; Group II-VI compounds, such as TeS; magnetic materials, such as NiFe; glasses, such as used, for example in flat panel displays; or any combination thereof, especially those substrates including: metal and/or metal alloy layers, optionally with via holes features for interconnect, such as layers containing aluminum, titanium, copper, and/or tungsten; oxide layers, such as silicon oxides; nitride layers, such as silicon nitride; and the like; or any combination thereof.
• the cleaning compositions of the present invention are also effective in removing organometallic and metal oxide residue generated on the substrate of etching equipment utilized in the fabrication of integrated circuits.
• etching equipment utilized in the fabrication of integrated circuits. Examples of commercially available etching equipment include that available from Lam Research, Tegal, Electrotech, Applied Materials, Tokyo Electron, Hitachi, and the like.
• Another aspect of the invention relates to a method of cleaning a substrate using the compositions of the present invention, which method involves contacting a substrate having organometallic and/or metal oxide residue thereon with a stripping and cleaning composition for a time and at a temperature sufficient to remove the residue.
• the residue is removed with no observable etching to the substrate, that is, with etch rates less than about 1 angstrom per minute of immersion at the operating conditions.
• the substrate can be immersed in the composition according to the invention.
• those substrates exposed to the residue removers of the present invention with the resultant very low etch rates can be salvaged, while those substrates immersed in more aggressive formulations are destroyed.
• the composition according to the invention can be applied to a surface of the substrate, e.g., by spraying on, applying droplets, coating, overcoating (with the excess composition running off the substrate), or the like, or a combination thereof.
• the low flash point and vapor pressure of the preferred compositions of this invention allow this type of application without resulting in unacceptable evaporation and vapors.
• the time and temperature of the contact between the composition and the substrate layer(s) can be determined based on the particular material being removed from a substrate.
• the useful temperature is in the range of from about ambient or room temperature to about 100°C and the contact time is typically from about 2 to about 60 minutes.
• the temperature range may expand to higher temperatures, especially when the flash point of the two-carbon atom linkage alkanolamine compound(s) are relatively high, as is the case when AEEA and/or DGA are included in the composition according to the invention.
• the flash point of a formulation is above the flash point of the component in the formulation with the lowest flash point, particularly if that component is freely miscible and is present in a minor quantity.
• compositions of this invention at temperatures between about 101°C and about 160°C, for example between about 115°C and about 150°C, alternatively from about 115°C to about 135°C. These higher temperatures can be used at atmospheric pressure and, of course, at superatmospheric pressure.
• the compositions allow use of the higher temperatures from a technical standpoint and also allow use of the compositions from a regulatory standpoint. Regulations generally become more stringent as operating temperatures approach a predetermined fraction of the flash point.
• the component with a boiling point below 150°C in selected preferred compositions, and which is also the component which is most volatile at operating temperatures, is water. Water can be easily replenished to the solution, and water does not present a safety hazard.
• the components with a boiling point below 150°C in other selected preferred compositions, which are most volatile at operating temperatures, are hydroxylamine and water. Water and hydroxylamine can be easily replenished to the solution, and this replentishing solution does not present a significant fire hazard.
• a replenishing solution may be combined with the original composition according to the invention to at least partially replenish the evaporated (and/or degraded) component(s) (and/or portion(s)) of the original composition.
• the replenishing composition contains water.
• the replenishing composition can contain polar organic solvent.
• the replenishing compositions according to the invention may optionally also contain, as necessary and where the original composition contained one or more of these components (or a portion thereof), at least one of the following: AEEA, at least one other two-carbon atom linkage alkanolamine compound, a base of the HF-base salt, a chelating agent and or a corrosion inhibitor, hydroxylamine or a hydroxylamine derivative, a surfactant, a non-hydroxyl-containing amine compound, and any combination thereof.
• the replenishing solutions of many embodiments of the present invention contain only water and optionally hydroxylamine or hydroxylamine derivative.
• the replenishing solutions of this embodiment are substantially free of polar organic solvents, alkanolamines, corrosion inhibitors, and chelators.
• a replenishing solution contains both the residue remover (to make up that which is for example lost in the wash) and additional compounds, then for purposes of this disclosure the replenishing solution contains only the additional ingredients.
• replenishing solutions of many embodiments of the present invention contain only water, optionally hydroxylamine or hydroxylamine derivative, and a corrosion
• the replenishing solutions of this embodiment are substantially free of polar organic solvents and alkanolamines.
• the replenishing solution contains only the additional ingredients.
• the replenishing solutions of many embodiments of the present invention contain water, AEEA, optionally hydroxylamine or hydroxylamine derivative, and optionally a corrosion inhibitor and/or chelating agent.
• AEEA optionally hydroxylamine or hydroxylamine derivative
• a corrosion inhibitor and/or chelating agent optionally a corrosion inhibitor and/or chelating agent.
• the AEEA:water ratio in the replenishing composition be not more than about
• the replenishing solution has a weight ratio of AEEA:water of not more than about 0.9:1, preferably not more than about 0.75:1, more preferably not more than about 0.5:1.
• the replenishing solutions are therefore 0 less expensive than prior art replenishing formulations, which typically contained a greater ratio of alkanolamines to water than was present in the original residue remover.
• the replenishing solutions of this embodiment are substantially free of polar organic solvents.
• the most prevalent component(s) (or portion(s) thereof) present in the replenishing compositions are those which have relatively low vapor pressures at operating temperatures, or those which have relatively low boiling points, at least in
• the replenishing composition can advantageously contain less than about 20% of, preferably can contain less than about 10% of, more preferably can contain less than about 5% of, alternately can be substantially free from, any component(s) (besides water) that has a boiling point of less than about 185°C,
• 35 preferably less than about 200°C, alternately less than about 215°C, and that has a flash point of less than about 95°C, preferably less than about 100°C, alternately less than about 110°C.
• both the original composition according to the invention and the replenishing composition contain AEEA and another two-carbon atom linkage alkanolamine compound with a boiling point below that of AEEA
• the AEEA: other alkanolamine ratio in the replenishing composition be not more than about 95%, preferably not more than about 80%, of the AEEA:other alkanolamine ratio in the original composition.
• the substrate may then be rinsed in a low-boiling-point polar organic solvent, such as isopropyl alcohol or N- methylpyrrolidone, or in a mildly acidic organic acid solution, such as acetic or citric acid, followed by a deionized water rinse.
• a low-boiling-point polar organic solvent such as isopropyl alcohol or N- methylpyrrolidone
• a mildly acidic organic acid solution such as acetic or citric acid
• the substrate may be merely rinsed with a very dilute solution of a carboxylic acid and deionized water, or even just with deionized water, especially if the composition according to the invention is substantially free of other alkanolamines and/or other alcohol amines.
• the substrate may then be rinsed in a low molecular weight polar solvent, such as isopropyl alcohol, followed by a deionized water rinse.
• a low molecular weight polar solvent such as isopropyl alcohol
• the substrate may then be rinsed in a mildly acidic organic acid solution, such as acetic or citric acid in water or water/alcohol, followed by a deionized water rinse.
• the substrate may be merely rinsed with deionized water, especially if the composition according to the invention contains AEEA and at most 10% (and preferably at most about 5%) of other alkanolamines and/or alcohol amines.
• the residue removing composition is substantially free of polar organic solvents, corrosion inhibitors, organic solvents (polar or non-polar), and chelating agents which are not readily miscible with water.
• the substrate can then be mechanically dried, such as with a spin drier, or nitrogen blow dried. Alternately or additionally, the substrate may be allowed to at least partially air dry and/or may be nominally heated
• Another aspect of the invention relates to a method of etching, and optionally cleaning, a substrate using the compositions of the present invention, which method involves contacting a substrate comprising a metal or metal alloy to be etched, and optionally having organometallic and/or metal oxide residue thereon, with the composition according to the invention for a time and at a temperature sufficient to selectively etch the metal or metal alloy, and optionally remove the residue.
• the etching formulation can advantageously contain an abrasive, or alternatively the substrate can be contacted with a rubbing surface having an abrasive thereon.
• the etch rate of the metal or metal alloy can be advantageously tailored by selecting an appropriate two-carbon atom linkage alkanolamine compound or mixture thereof, based on the metal or metal alloy to be etched. For example, with an aluminum- or titamum-containing substrate, a relatively low etch rate can be obtained in most embodiments of this invention with the two-carbon atom linkage alkanolamine compound being only AEEA, whereas the etch rate can be incrementally increased by maintaining the same total percentage of two-carbon atom linkage alkanolamine compound, but by incrementally decreasing the proportion of AEEA with respect to, e.g., DGA.
• the substrate can be immersed in the composition according to the invention.
• the composition according to the invention can be applied to a surface of the substrate, e.g., by spraying on, applying droplets, coating, overcoating (with the excess composition running off the substrate), or the like, or a combination thereof.
• the etching formulation can advantageously contain an abrasive and be contacted with a smooth surface, or alternatively the substrate can be contacted with a rubbing surface having an abrasive thereon.
• the time and temperature are determined based on the particular material being removed from a substrate.
• the temperature is in the range of from about ambient or room temperature to about 120°C and the contact time is typically from about 2 to about 60 minutes.
• the temperature range may expand to higher temperatures, especially when the flash point of the two-carbon atom linkage alkanolamine compound(s) are relatively high, as is the case when AEEA and/or DGA are included in the composition according to the invention.
• FIG. 1 is a scanning electron microscope (SEM) photograph of the wafer after this treatment. Substantial undercutting of both Ti layers are visible in this photograph.
• FIG. 2 is a SEM photograph of the wafer after this treatment. No undercutting of the lower Ti layer is visible, and a slight undercutting of the upper Ti layer is visible.
• FIG. 3 is a SEM photograph of the wafer after this treatment. Undercutting of both Ti layers is visible.
• Example 4
• FIG.4 is a SEM photograph of the wafer after this treatment. A slight undercutting of the lower Ti layer is visible, and no undercutting of the upper Ti layer is visible.
• FIG. 5 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layer is visible.
• Example 6 A semiconductor wafer having a patterned metal stack consisting of
• TiN/Ti/Al/Ti/TiN/BPSG boron phosphosilicate glass
• composition F boron phosphosilicate glass
• FIG. 7 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layers is visible.
• FIG. 8 is SEM photograph of the wafer after this treatment. Undercutting of the Ti layers is visible.
• compositions B, D, E, F and G successfully remove residues from substrates having a titanium metallurgy with only moderate attack on the titanium metallurgy.
• Increased amounts of catechol or gallic acid produce an improved reduction of attack on the titanium metallurgy.
• the comparative compositions A, C and H all show substantial attack on the titanium metallurgy, even when a two carbon atom linkage alkanolamine compound is used in the absence of gallic acid or catechol.
• gallic acid or catechol is used with an alkanolamine compound other than a two carbon atom linkage alkanolamine compound, the gallic acid or catechol does not show a proportionate reduction of attack of the composition on the titanium metallurgy.
• Table 2 below describes cleaning compositions 1 through 14 for Examples 9-20 to follow.
• FIG. 9A shows the patterned feature after etching processes examining under a Scanning Electron Microscope, Hitachi SEM 6400.
• the patterned substrate was then immersed in separate beakers containing Compositions 1 and 2 for 60 minutes at 75 °C.
• the substrates were then rinsed in deionized water and were dried by blowing nitrogen across the substrate surfaces.
• the patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 9B and 9C show the result after the cleaning processes. SEM inspection of these patterned wafers also support the conclusions that AEEA-containing hydroxylamine formulations do not attack the sensitive titanium layer, while DGA-containing hydroxylamine formulations do attack the sensitive titanium layer when contacted under those conditions.
• Example 10 Study of Corrosion of Metal Film with Different AEEA Mixtures This example illustrates that AEEA can be formulated with other solvents and water without causing detrimental attack on the substrate film.
• Composition 4 is a mixture of AEEA and NMP, a common polar solvent used by the semiconductor industry as a photoresist stripper.
• Composition 5 is a mixture of AEEA, DMAC, and Catechol.
• Composition 6 is a 85% AEEA with 15% water solution.
• Etch rates of less than about 2 angstroms per minute are acceptable for many applications, but etch rates of 1 angstrom or less per minute, preferably 0.5 angstroms or less per minute, are preferred. It was surprising that a composition containing 85% AEEA with 15% water solution did not etch either aluminum or titanium. These metals have been known to etch when contacted with amines and water.
• Example 11 Demonstration of Wide Process Window for AEEA
• a lower aggressiveness of AEEA to sensitive metals widens the available process window (time, temperature) for cleaning.
• Optimum process condition and composition of DGA-containing remover solutions can be developed to minimize the metal attack, such as in Compositions 2, 8, and 10, which include at least one commercial formulation.
• the use of AEEA in a weight-for- weight substitution with DGA in Compositions 1, 7, and 9 showed less dependency on process conditions and less etch rate on both aluminum and titanium, while still maintaining compatibility with the substrate metal film. See Table 5 below.
• dielectric layers are not attached by the AEEA formulations.
• AEEA can be used with gallic acid (Compositions 11 and 13) to obtain good compatibility, i.e., low etch rates, with the substrate aluminum and titanium metal films, as shown in Table 6 below. Increasing gallic acid from 2.5% to 7.5% moderately further reduces etch rates. Similar results are expected with gallic acid derivatives. Similar results are also expected with N,N-diethyl-hydroxylamine.
• Example 13 Tungsten Compatibility
• tungsten film was deposited on a silicon wafer surface using conventional semiconductor manufacturing processes.
• the thicknesses of the metal film were measured with a 4-Dimension Four Point Probe, Model 280, to determine the initial thickness of the metal film.
• Two solutions with different amounts of AEEA were mixed in a separate beakers according to Compositions 13 and 14. These solutions were maintained in separate beakers and heated to 65°C. Samples of the tungsten substrate were then totally immersed into the solution and maintained at 65°C for 20 minutes. The samples were then taken out from the solution and immediately rinsed with deionized water to remove all the chemical solutions. The sample was then dried by blowing dry nitrogen across the surface. The thickness of the metal film was then measured again in the Four Point Probe to obtain the final thickness.
• Table 7 shows these compositions having minimum tungsten attack.
• Compatibility with tungsten has become increasingly important to the semiconductor manufacturing process. As the device geometry gets smaller, the metal overlay on the tungsten may be misaligned and may expose the surface, which situation is commonly referred as "exposed tungsten plug.”
• Figures 17A and 17B are SEM photographs of just such a misalignment. If the chemistry is too aggressive toward tungsten, the tungsten can be eroded or corroded and can cause disconnection of any wiring present on the substrate, as shown in Figure 17C.
• a barrier or adhesion layer such as titanium (Ti), titanium nitride (TiN), titanium tungsten (TiW), tantalum nitride (TaN), or the like, can be deposited on a dielectric surface, such as silicon, silicon dioxide, or the like;
• a metal conducting layer such as copper, aluminum, or aluminum alloys, e.g. , with silicon and/or copper can then be deposited over the barrier or adhesion layer; 3.
• the surface of the metal layer can then be capped with a layer of titanium, titanium nitride, titanium tungsten, silicon oxynitride (SiON), or a combination of these thin film, as an antireflective coating;
• a photoresist can then be spin coated over the metal stack film and patterned using the conventional lithography tools, e.g., such as manufacturing by Cannon, Nikon, ASML, Ultratech Stepper, etc.;
• the pattern can then be transferred to the film stack by plasma etching processes, e.g., using etching equipment from Applied Materials, Lam Research, TEGAL, TEL, etc.;
• the resist mask can be removed by oxygen plasma ashing either in situ (on the etching equipment) or in a separate oxygen plasma asher produced by, e.g., Mattson, Gasonics, Matrix, etc.; and
• the substrate can then be processed by cleaning with a solution, such as the composition according to the invention.
• the patterned substrate may be exposed to the solution by either i. directly immersing the substrate wafer into a bath of the chemical solutions, which is maintained at a constant temperature, ranging from room temperature to about 15°C below the flash point of the most volatile/dangerous component, or ii. Bringing the chemical solution to the wafer surface by dispensing the chemical solution at an operating temperature, ranging from room temperature to about 15°C below the flash point of the most volatile/dangerous component, into a chamber where it can hold either a single wafer or cassettes of wafers.
• the substrates can then be rinsed in deionized water, if necessary, until the resistivity of the deionized water returned to at least about 18M ⁇ , which is usually as the end point detection for wafer cleanliness.
• an intermediate rinse can be performed with a solvent, e.g. , such as isopropyl alcohol, N-methyl-2 pyrrolidone, a dilute solution of organic acids (such as citric acid, acetic acid etc.), or a combination thereof, followed by deionized water.
• a solvent e.g. , such as isopropyl alcohol, N-methyl-2 pyrrolidone, a dilute solution of organic acids (such as citric acid, acetic acid etc.), or a combination thereof, followed by deionized water.
• the wafer substrates can then be dried by blowing dry nitrogen across the surface, while rotating the wafer singly (single wafer process) or in a cassette (batch wafer process).
• a layer of insulating material e.g. , such as silicon dioxide, fluorinated silicon dioxide, carboneous silicon dioxide, a low dielectric organic material (such as polyimide, SILKTM, etc.), or the like, can be deposited over a patterned metal surface to a desired thickness;
• interlayer dielectric (ILD) material which may have a via hole with a structure for interconnection, can then be planarized by processes such as chemical mechanical planarization (CMP), chemical etch back, etc.;
• a photoresist can then be spin coated over the ILD film and patterned using conventional lithography tools, such as manufacturing by Cannon, Nikon, ASML, Ultratech Stepper, etc.;
• the pattern can then be transferred to the ILD film by plasma etching processes e.g. , using etching equipment from Applied Materials, Lam Research, TEGAL, TEL, etc.;
• the resist mask can be removed by oxygen plasma ashing either in situ (on the etching equipment) or in a separate oxygen plasma asher produced by, e.g., Mattson, Gasonics, Matrix, etc.; and
• the substrate can then be processed by cleaning with a solution, such as the composition according to the invention.
• the patterned substrate may be exposed to the solution by either i. directly immersing the substrate wafer into a bath of the chemical solutions, which is maintained at a constant temperature, ranging from room temperature to about 15°C below the flash point of the most volatile/dangerous component, or ii. Bringing the chemical solution to the wafer surface by dispensing the chemical solution at an operating temperature, ranging from room temperature to about 15°C below the flash point of the most volatile/dangerous component, into a chamber where it can hold either a single wafer or cassettes of wafers.
• the substrates can then be rinsed in deionized water, if necessary, until the resistivity of the deionized water returned to at least about 18M ⁇ , which is usually as the end point detection for wafer cleanliness.
• an intermediate rinse can be performed with a solvent, e.g., such as isopropyl alcohol, N-methyl-2 pyrrolidone, a dilute solution of organic acids (such as citric acid, acetic acid etc.), or a combination thereof.
• the wafer substrates can then be dried by blowing dry nitrogen across the surface, while rotating the wafer singly (single wafer process) or in a cassette (batch wafer process). These processes were used for Examples 14-21 below.
• Figure 10A demonstrates an examination under a Scanning Electron Microscope, Hitachi SEM 6400, which shows the patterned feature of a composite of films of -500A TiN/ ⁇ 500 ⁇ A A1/-250A TiN/ ⁇ l OOA Ti after etching processes according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 1, 2, and 3 for 20 minutes at 70°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 10B, 10C and 10D show the result after the cleaning processes. Composition 1 effectively removed all the etch residues from the substrate surface with no evidence of attack of the substrate.
• Example 15 Comparison of Etch Residue Removal Performance For Example 15, Figure 11 A demonstrates an examination under a Scanning
• Figure 12A demonstrates an examination under a Scanning Electron Microscope, Hitachi SEM 6400, which shows the patterned feature of a composite of films of ⁇ 25 ⁇ A TiN/ ⁇ 700 ⁇ A Al/ ⁇ 50 ⁇ A TiN after etching processes according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 1, 2, and 3 for 20 minutes at 70°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 12B, 12C, and 12D show the result after the cleaning processes. Composition 1 with AEEA effectively removed all the etch residues from the substrate surface.
• Figure 13A demonstrates an examination under a Scanning Electron Microscope, Hitachi SEM 6400, which shows the patterned feature of a composite of a pad film of -500A SiON/ ⁇ 14,OO ⁇ A A1 O0OA TaN after etching processes according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 11 and 13 for 30 minutes at 70°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 13B and 13C show the result after the cleaning processes. Composition 13 effectively removed all the etch residues from the substrate surface without pitting the metal surface.
• Figure 14A demonstrates an examination under a Scanning
• Electron Microscope, Hitachi SEM 6400 which shows the patterned feature of a composite of film of -400A TiN/ ⁇ 450 ⁇ A A1/-800A TiN OOA Ti after etching processes according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 7 and 8 for 60 minutes at 70°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 14B and 14C show the result after the cleaning processes. Composition 7 with AEEA effectively removed all the etch residues from the substrate surface without attacking metal surface as much as Composition 8 with DGA.
• Figure 15A demonstrates an examination under a Scanning Electron Microscope, Hitachi SEM 6400, which shows the patterned feature of a composite of film of ⁇ 50 ⁇ A TiN/ ⁇ l 1,000A A1/-800A Ti after etching processes according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 9 and 10 for 60 minutes at 75°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 15B and 15C show the result after the cleaning processes. Composition 9 with AEEA effectively removed all the etch residues from the substrate surface without attacking metal surface as much as Composition 10 with DGA and MEA.
• Figure 16A demonstrates an examination under a Scanning Electron Microscope, Hitachi SEM 6400, which shows the via hole patterned feature after etching processes according to general procedures described above. Post-etch residue remained on inside surface.
• the patterned substrate was then immersed in separate beakers containing Composition 7 and 8 for 30 minutes at 65°C. The substrates were then rinsed in deionized water and dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 16B and 16C show the result after the cleaning processes. Composition 7 effectively removed all the etch residues from the substrate surface without attacking metal surface.
• Table 8 below describes cleaning compositions 15 through 21 for Examples 22-24 to follow, as well as prophetic compositions 22 through 30. The processes described above for Examples 14-21 are also used in Examples 22-24.
• Ethylenediaminetetraacetic acid or a salt thereof EDTA
• Example 22 Comparison of Etch Residue Removal Performance Between AEEA and DGA in Hvdroxyl--mine-Containing Compositions
• composites of film having an external titanium and an external aluminum layer, respectively were patterned and subject to etching under process conditions according to general procedures described above.
• the patterned substrate was initially examined under a Scanning Electron Microscope, Hitachi SEM 6400. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 15 and 16 for 20 minutes at 65°C.
• the substrates were then rinsed in deionized water and then dried by blowing nitrogen across the substrate surfaces.
• the patterned substrate was then inspected again using Hitachi SEM 6400. Compositions 15 and 16 effectively removed all the etch residues from the substrate surface. See Table 9 for results.
• Example 23 Comparison of Etch Residue Performance Between Freshly Mixed and Used Compositions Containing AEEA. Hydroxylamine. and Another Two-Carbon
• composites of film having an external titanium and an external aluminum layer, respectively, were patterned and subject to etching under process conditions according to general procedures described above.
• the patterned substrate was initially examined under a Scanning Electron Microscope, Hitachi SEM 6400. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beakers containing Compositions 17 and 18 for 20 minutes at 65°C. The substrates were then rinsed in deionized water and then dried by blowing nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Example 24 Comparison of Etch Residue Removal Performance in Compositions Containing Hydroxylamine and AEEA. DGA. or Both For example 24, composites of film having an external titanium and an external aluminum layer, respectively, are patterned and subject to etching under process conditions according to general procedures described above. The patterned substrate is
• Composition 19 effectively remove all the etch residues from the substrate surface without attacking the aluminum surface, as compared to Composition 20.
• Composition 21 showed an intermediate result for the aluminum surface, but a superior result for the titanium surface, suggesting synergy between AEEA and DGA in selected cases. See Table 10 for results.
• Example 25 The Effect of AEEA on the Erosion of Tungsten in the Presence of Aluminum. 35
• Figure 18A demonstrates an examination under a Scanning
• Electron Microscope Hitachi 6400, showing an exposed tungsten plug on the patterned features of a metal film after etching process according to general procedures described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in separate beaker containing Compositions 1, 2, and 10 for 60 minutes at 70°C. The substrates were rinsed in deionized water and dried by blowing dry nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 18B, 18C, and 18D show the result after each of the cleaning processes on Compositions 1, 2, and 10, respectively.
• Composition 1, containing AEEA effectively removed the etch residue from the metal surface without eroding the tungsten plug and attacking the aluminum surface.
• Composition 2 attacked the titanium layer and lifted the metal line off ( Figure 18D), and Composition 10 severely attacked the aluminum surface ( Figure 18C).
• Example 26 The Effect of Gallic Acid on Aqueous AEEA Compositions.
• Figure 19A demonstrates an examination under a Scanning Electron Microscope, Hitachi 6400, showing a patterned feature of a composite film of ⁇ 25 ⁇ A TiN/ ⁇ 700 ⁇ A Al/ ⁇ 50 ⁇ A TiN after etching processes according to general procedure described above. Post-etch residue remained on the metal line surface.
• the patterned substrate was then immersed in a separate beaker containing Compositions 6 and 15 for 20 minutes at 75°C. The substrates were rinsed in deionized water and dried by blowing dry nitrogen across the substrate surfaces. The patterned substrate was then inspected again using Hitachi SEM 6400.
• Figures 19B and 19C show the results after each of the cleaning processes. Composition 6, containing AEEA and water, ( Figure 19B) and Composition 15 ( Figure 19C) were capable of effectively removing post-etch residues.
• formulations containing AEEA and one or more of: polar organic solvents, water, an amine, other alkanolamines, chelators, and corrosion inhibitors provide excellent removal of etch residue from copper and copper alloy substrates with low, commercially acceptable rates of etching.
• the formulations are substantially free of hydroxylamine. Hydroxylamine in many formulations is aggressive to copper.
• hydroxylamine derivatives in which alkyl groups may partially shield the function group(s)
• AEEA hydroxylamine derivatives
• one or more of water, polar organic solvents, chelating agent, corrosion inhibitors e.g., benzotriazole, which is well-known for its non- aggressiveness toward copper layers
• corrosion inhibitors e.g., benzotriazole, which is well-known for its non- aggressiveness toward copper layers

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